Pyrolysis-catalysis upcycling of waste plastic using a multilayer stainless-steel catalyst toward a circular economy.

Current un-sustainable plastic management is exacerbating plastic pollution, an urgent shift is thus needed to create a recycling society. Such recovering carbon (C) and hydrogen (H) from waste plastic has been considered as one practical route to achieve a circular economy. Here, we performed a simple pyrolysis-catalysis deconstruction of waste plastic via a monolithic multilayer stainless-steel mesh catalyst to produce multiwalled carbon nanotubes (MWCNTs) and H2, which are important carbon material and energy carrier to achieve sustainable development. Results revealed that the C and H recovery efficiencies were as high as 86% and 70%, respectively. The unique oxidation-reduction process and improvement of surface roughness led to efficient exposure of active sites, which increased MWCNTs by suppressing macromolecule hydrocarbons. The C recovery efficiency declined by only 5% after 10 cycles, proving the long-term employment of the catalyst. This catalyst can efficiently convert aromatics to MWCNTs by the vapor-solid-solid mechanism and demonstrate good universality in processing different kinds of waste plastics. The produced MWCNTs showed potential in applications of lithium-ion batteries and telecommunication. Owing to the economic profits and environmental benefits of the developed route, we highlighted its potential as a promising alternative to conventional incineration, simultaneously achieving the waste-to-resource strategy and circular economy.

Benign-by-design plant extract-mediated preparation of copper oxide nanoparticles for environmentally related applications.

A facile, cost-competitive, scalable and novel synthetic approach is used to prepare copper oxide (CuO) nanoparticles (NPs) using Betel leaf (Piper betle) extracts as reducing, capping, and stabilizing agents. CuO-NPs were characterized using various analytical techniques, including Fourier-transform infrared (FTIR) spectroscopy, ultraviolet-visible (UV-Vis) spectroscopy, scanning electron microscopy (SEM), X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), as well as photoluminescence (PL) measurements. The activity of CuO-NPs was investigated towards Congo red dye degradation, supercapacitor energy storage and antibacterial activity. A maximum of 89% photodegradation of Congo red dye (CR) was obtained. The nanoparticle modified electrode also exhibited a specific capacitance (Csp) of 179 Fg-1. Furthermore, the antibacterial potential of CuO NPs was evaluated against Bacillus subtilis and Pseudomonas aeruginosa, both strains displaying high antibacterial performance.

Imidazolate framework material for crude oil removal in aqueus media: Mechanism insight.

Considerable amount of produced water discharged by the oil industry contributes to an environmental imbalance due to the presence of several components potentially harmful to the ecosystem. We investigated the factors influencing the adsorption capacity of Zinc Imidazolate Framework-8 (ZIF-8) in finite bath systems for crude oil removal from petroleum extraction in synthetic produced water. ZIF-8, experimentally obtained by solvothermal method, was characterized by XRD, FTIR, TGA, BET and its point of zero charge (pHpcz) was determined. Synthesized material showed high crystallinity, with surface area equal to 1558 m2 g-1 and thermal stability equivalent to 400 °C. Adsorption tests revealed, based on the Sips model, that the process takes place in a heterogeneous system. Additionally, intraparticle diffusion model exhibited multilinearity characteristics during adsorption process. Thermodynamic investigation demonstrated that adsorption process is spontaneous and exothermic, indicating a physisorption phenomenon. These properties enable the use of ZIF-8 in oil adsorption, which presented an adsorption capacity equal to 452.9 mg g-1. Adsorption mechanism was based on hydrophobic interactions, through apolar groups present on ZIF-8 structure and oil hydrocarbons, and electrostatic interactions, through the difference in charges between positive surface of adsorbent and negatively charged oil droplets.

Association of a dietary inflammatory index with cardiometabolic, endocrine, liver, renal and bones biomarkers: cross-sectional analysis of the UK Biobank study.

BACKGROUND AND AIMS: Research into the relationship between an Energy-adjusted Diet-Inflammatory Index (E-DII) and a wider health-related biomarkers profile is limited. Much of the existing evidence centers on traditional metabolic biomarkers in populations with chronic diseases, with scarce data on healthy individuals. Thus, this study aims to investigate the association between an E-DII score and 30 biomarkers spanning metabolic health, endocrine, bone health, liver function, cardiovascular, and renal functions, in healthy individuals. METHODS AND RESULTS: 66,978 healthy UK Biobank participants, the overall mean age was 55.3 (7.9) years were included in this cross-sectional study. E-DII scores, based on 18 food parameters, were categorised as anti-inflammatory (E-DII < -1), neutral (-1 to 1), and pro-inflammatory (>1). Regression analyses, adjusted for confounding factors, were conducted to investigate the association of 30 biomarkers with E-DII. Compared to those with an anti-inflammatory diet, individuals with a pro-inflammatory diet had increased levels of 16 biomarkers, including six cardiometabolic, five liver, and four renal markers. The concentration difference ranged from 0.27 SD for creatinine to 0.03 SD for total cholesterol. Conversely, those on a pro-inflammatory diet had decreased concentrations in six biomarkers, including two for endocrine and cardiometabolic. The association range varied from -0.04 for IGF-1 to -0.23 for SHBG. CONCLUSION: This study highlighted that a pro-inflammatory diet was associated with an adverse profile of biomarkers linked to cardiometabolic health, endocrine, liver function, and renal health.

The Role of Surface Complexes in Ketene Formation from Fatty Acids via Pyrolysis over Silica: from Platform Molecules to Waste Biomass.

Fatty acids (FA) are the main constituents of lipids and oil crop waste, considered to be a promising 2G biomass that can be converted into ketenes via catalytic pyrolysis. Ketenes are appraised as promising synthons for the pharmaceutical, polymer, and chemical industries. Progress in the thermal conversion of short- and long-chain fatty acids into ketenes requires a deep understanding of their interaction mechanisms with the nanoscale oxide catalysts. In this work, the interactions of fatty acids with silica are investigated using a wide range of experimental and computational techniques (TPD MS, DFT, FTIR, in situ IR, equilibrium adsorption, and thermogravimetry). The adsorption isotherms of linear and branched fatty acids C1-C6 on the silica surface from aqueous solution have been obtained. The relative quantities of different types of surface complexes, as well as kinetic parameters of their decomposition, were calculated. The formation of surface complexes with a coordination bond between the carbonyl oxygens and silicon atoms in the surface-active center, which becomes pentacoordinate, was confirmed by DFT calculations, in good agreement with the IR feature at ∼1680 cm 1. Interestingly, ketenes release relate to these complexes' decomposition as confirmed by the thermal evolution of the absorption band (1680 cm-1) synchronously with the TPD peak of the ketene molecular ion. The established regularities of the ketenezation are also observed for the silica-induced pyrolysis of glyceryl trimyristate and real waste, rapeseed meals.

Rational Modulation of Single Atom Coordination Microenvironments in a BCN Monolayer for Multifunctional Electrocatalysis.

Single-atom (SA) catalysts (SACs) have demonstrated outstanding catalytic performances toward plenty of relevant electrochemical reactions. Nevertheless, controlling the coordination microenvironment of catalytically active SAs to further enhance their catalytic oerformences has remained elusive up to now. Herein, a systematic investigation of 20 transition metal atoms that are coordinated with 20 different microenvironments in a boroncarbon-nitride monolayer (BCN) is conducted using high-throughput density functional theory calculations. The experimentally synthesized ternary BCN monolayer contains carbon, nitrogen, and boron atoms in its 2D network, thus providing a lot of new coordination environments than those of the current Cx Ny nanoplatforms. By exploring the structural/electrochemical stability, catalytic activity, selectivity, and electronic properties of 400 (20 × 20) TM-BCN moieties, it is discovered that specific SA coordination environments can achieve superior stability and selectivity for different electrocatalytic reactions. Moreover, a universal descriptor to accelerate the experimental process toward the synthesis of BCN-SACs is reported. These findings not only provide useful guidance for the synthesis of efficient multifunctional BCN-SACs but also will immediately benefit researchers by levering up their understanding of the mechanistic effects of SA coordination microenvironments on electrocatalytic reactions.

Diagnostic accuracy of anthropometric indices for metabolically healthy obesity in child and adolescent population.

BACKGROUND: A variable percentage of children and adolescents with obesity do not have cardiometabolic comorbidities. A phenotype called metabolically healthy obese (MHO) has emerged to describe this population subgroup. Early identification of this condition may prevent the progression to metabolically unhealthy obesity (MUO). MATERIAL AND METHODS: A cross-sectional descriptive study of 265 children and adolescents from Cordoba (Spain) conducted in 2018. The outcome variables were MHO, established based on three criteria: International Criterion, HOMA-IR, and a combination of the previous two. RESULTS: The prevalence of MHO ranged from 9.4% to 12.8% of the study population, between 41% and 55.7% of the sample with obesity. The highest agreement was reached between the HOMA-IR definitions and the combined criteria. The waist-to-height ratio (WHtR) was the indicator with the highest discriminant capacity for MHO in 2 of the three criteria, with its best cut-off point at 0.47 for both. CONCLUSION: The prevalence of MHO in children and adolescents differed according to the criteria used for diagnosis. The anthropometric variable with the most remarkable discriminating capacity for MHO was WHtR, with the same cut-off point in the three criteria analysed. IMPACT STATEMENT: This research work defines the existence of metabolically healthy obesity through anthropometric indicators in children and adolescents. Definitions that combine cardiometabolic criteria and insulin resistance are used to identify metabolically healthy obesity, as well as the prediction of this phenomenon through anthropometric variables. The present investigation helps to identify metabolically healthy obesity before metabolic abnormalities begin.

An eco-friendly approach on green synthesis, bio-engineering applications, and future outlook of ZnO nanomaterial: A critical review.

Synthesizing ZnO nanostructures ranging from 1 nm to 4 nm confines the electron cloud and exhibits a quantum effect generally called as quantum confinement effect attracting many researchers in the field of electronics and optics. ZnO nanostructures are used in medical applications to formulate antioxidant, antibacterial, antifungal, anti-inflammatory, wound healing, and anti-diabetic medications. This work is a comprehensive study of green synthesis of ZnO nanomaterials using different biological sources and highlights different processes able to produce nanostructures including nanowires, nanorods, nanotubes and other nano shapes of ZnO nanostructures. Different properties of ZnO nanostructures and their targeted bioengineering applications are also described. The strategies and challenges of the eco-friendly approach to enhance the application span of ZnO nanomaterials are also summarized, with future prospects for greener design of ZnO nanomaterials are also suggested.

Design of tropinium-functionalized anion exchange membranes for acid recovery via diffusion dialysis process.

Diffusion dialysis (DD) process utilizing anion exchange membranes (AEMs) is an environmentally-friendly and energy-efficient technology. From acidic wastewater, DD is needed for acid recovery. This research reports the development of a series of dense tropinium-functionalized AEMs via solution casting method. Fourier Infrared transform (FTIR) spectroscopy verified the successful preparation of AEMs. The developed AEMs exhibited a dense morphology, featuring 0.98-2.42 mmol/g of ion exchange capacity (IEC), 30-81% of water uptake (WR) and 7-32% of linear swelling ratio (LSR). They displayed exceptional mechanical, thermal and chemical stability and were employed for acid waste treatment from HCl/FeCl2 mixtures via DD process. AEMs possessed 20 to 59 (10-3 m/h) and 166 to 362 of acid diffusion dialysis coefficient (UH+) and separation factor (S) respectively at 25 °C. Compared to DF-120 commercial membrane (UH+ = 0.004 m/h, S = 24.3), their DD efficiency was improved under identical experimental conditions.

Recent advances in the remediation of perfluoroalkylated and polyfluoroalkylated contaminated sites.

Per- and polyfluoroalkyl substances (PFASs) are compounds used since 1940 in various formulations in the industrial and consumer sectors due to their high chemical and thermal stability. In recent years, PFASs have caused global concern due to their presence in different water and soil matrices, which threatens the environment and human health. These compounds have been reported to be linked to the development of serious human diseases, including but not limited to cancer. For this reason, PFASs have been considered as persistent organic compounds (COPs) and contaminants of emerging concern (CECs). Therefore, this work aims to present the advances in remediation of PFASs-contaminated soil and water by addressing the current literature. The performance and characteristics of each technique were addressed deeply in this work. The reviewed literature found that PFASs elimination studies in soil and water were carried out at a laboratory and pilot-scale in some cases. It was found that ball milling, chemical oxidation and thermal desorption are the most efficient techniques for the removal of PFASs in soils, however, phyto-microbial remediation is under study, which claims to be a promising technique. For the remediation of PFASs-contaminated water, the processes of electrocoagulation, membrane filtration, ozofractionation, catalysis, oxidation reactions - reduction, thermolysis and destructive treatments with plasma have presented the best results. It is noteworthy that hybrid treatments have also proved to be efficient techniques in the removal of these contaminants from soil and water matrices. Therefore, the improvisation and implication of existing techniques on a field-scale are greatly warranted to corroborate the yields obtained on a pilot- and laboratory-scale.

Investigation on synthesis of ternary g-C3N4/ZnO-W/M nanocomposites integrated heterojunction II as efficient photocatalyst for environmental applications.

The rapid industrialization of the world is disparagingly manipulating our environment and natural ecosystem. The researchers are taking keen interest to invent novel material as photocatalyst for non-degradable organic pollutants. Solar energy-driven practices employing semiconductors are a novel approach towards wastewater remediation. Here in, we successfully synthesized a vigorous photocatalysts comprising of g-C3N4 and doped ZnO-W/M (M = Co, Ce, Yb, Sm) by co-precipitation followed by metals doping via calcination approach. The structural, morphological, and photocatalytic applications for organic pollutants of synthesized heterostructure nanocomposites were examined by XRD, FTIR, SEM, EDX and UV visible spectrophotometer. Diffraction peaks attributed to both g-C3N4 and ZnO-W were detected in the XRD spectra. The FTIR spectra also inveterate the formation of g-C3N4/ZnO-W/M composites. The SEM images reveal an agglomerated morphology and EDS analysis also confirmed close contact between g-C3N4, ZnO-W and doped metals. The abridged energy band gap of g-C3N4/ZnO-W/M (M = Ce, Yb, Sm, Co) nanocomposites calculated via Tauc plot are 2.68, 2.88, 3.24 and 3.29 eV respectively. Narrowing of bandgap is considered an imperative triumph for the degradation of industrial effluents. The photocatalytic activity was performed against four different dyes and follows the trend Ce > Yb > Sm > Co. The recyclability tests were carried out for different dyes and no substantial catalytic activity loss was observed even after the fourth experimental run, which proves that reported ternary heterojunctions exhibit high mechanical stability and reusability.The species trapping experiment exposed that generated h+ are the principal active specie for dye photodegradation reactions. This work disseminates a novel photocatalyst for the removal of synthetic dyes.

MOF@biomass hybrids: Trends on advanced functional materials for adsorption.

This contribution aims to demonstrate the scope of new hybrids between biomass and metal-organic frameworks (MOF@biomass) used in the adsorption process of pollutants. After a brief presentation of the use of the main series of MOFs as efficient adsorbents for different types of pollutants, the limitations of these structures related to particle size and hydrodynamic problems during their application are highlighted. Lignocellulosic biomasses are also recognized as an alternative adsorbent, mainly due to their high natural abundance and their low environmental impact during and after their application. The limited capacity of bioadsorbents becomes important in this research. Consequently, the largest amount of information existing in the last ten years on MOF-Biomass functionalization as a hybrid and improvement technology for adsorption processes is compiled, analyzed, compared and contrasted. So far, there is no evidence of works that exploit the concept of functionalization of adsorbents of different nature to give rise to new hybrid materials. Through this review it was found that the hybrids obtained show a higher adsorption capacity (Qe) compared to their precursors, due to the increase of organic functional groups provided by the biomass. Thus, for heavy metals, dyes, Arsenium anions and other organic and pharmaceutical compounds, there are increases in Qe of about 100 mg g-1. The possibility of the new hybrid being studied for desorption and reuse processes is also raised, resulting in a new line of research that is attractive for the industry from an economic and environmental point of view. The functionalization methods and techniques used in the studies cited in this article are outlined. In conclusion, this research brings a new horizon of study in the field of adsorption and mentions the main future challenges related to new sustainable applications.

Covalent organic frameworks (COFs) core@shell nanohybrids: Novel nanomaterial support towards environmental sustainability applications.

Covalent organic frameworks (COFs) based on core@shell nanohybrids have recently received significant attention and have become one of the most promising strategies for improving the stability and catalytic activity of COFs. Compared with traditional core@shell, COF-based core@shell hybrids own remarkable advantages, including size-selective reactions, bifunctional catalysis, and integration of multiple functions. These properties could enhance the stability and recyclability, resistance to sintering, and maximize the electronic interaction between the core and the shell. The activity and selectivity of COF-based core@shell could be simultaneously improved by taking benefit of the existing synergy between the functional encapsulating shell and the covered core material. Considering that, we have highlighted various topological diagrams and the role of COFs in COF-based core@shell hybrid for activity and selectivity enhancement. This concept article provides all-inclusive advances in the design and catalytic applications of COF-based core@shell hybrids. Various synthetic techniques have been developed for the facile tailoring of functional core@shell hybrids, including novel seed growth, in-situ, layer-by-layer, and one-pot method. Importantly, charge dynamics and structure-performance relationships are investigated through different characterization techniques. Different COF-based core@shell hybrids with established synergistic interactions have been detailed, and their influence on stability and catalytic efficiency for various applications is explained and discussed in this contribution. A comprehensive discussion on the remaining challenges associated with COF-based core@shell nanoparticles and research directions has also been provided to deliver insightful ideas for additional future developments.

Silica-derived materials from agro-industrial waste biomass: Characterization and comparative studies.

The management and final disposal of agro-industrial wastes are one of the main environmental problems. Due to the presence of silica in some agricultural by-products, it is possible to convert waste into materials with advanced properties. This contribution was aimed to extract and characterize silica materials from various feedstocks including sugarcane bagasse (SCB), corn stalk (CS), and rice husk (RH). Silica yields of 17.91%, 9.39%, and 3.25% were obtained for RH, CS, and SCB. On the other hand, the textural properties show that the siliceous materials exhibited mesoporous structures, with high silica composition in the materials due to the formation of crystalline SiO2 for SCB and CS and amorphous for RH. XPS spectra demonstrate the presence of Si4+ species in RH, and Si3+/Si4+ tetrahedra in SCB and CS.

Valorization of sewage sludge for facile and green wood bio-adhesives production.

A method is presented herein for the design of wood bio-adhesives using sewage sludge extracts (SSE). SSE was extracted from SS using deep eutectic solvents and processed with glycerol triglycidyl ether (GTE) to disrupt the secondary structure of proteins. An additive was also used to improve mechanical performance. The resulting bio-adhesive (SSE/GTE@TA) had a wet shear strength of 0.93 MPa, meeting the Chinese national standard GB/T 9846-2015 (≥0.7 MPa). However, the high polysaccharide content in SSE would weaken the mechanical properties of wood bio-adhesives. The key to improve bio-adhesive quality was the formation of a strong chemical bond via Maillard reaction as well as higher temperatures (140 °C) to reduce polysaccharide content via dehydration. This approach has lower environmental impact and higher economic efficiency compared to incineration and anaerobic digestion of sewage sludge. This work provides a new perspective on the high-value utilization of SS and offers a novel approach to developing bio-adhesives for the wood industry.

Polymeric membranes functionalized with nanomaterials (MP@NMs): A review of advances in pesticide removal.

The excessive contamination of drinking water sources by pesticides has a pernicious impact on human health and the environment since only 0.1% of pesticides is utilized effectively to control the and the rest is deposited in the environment. Filtration by polymeric membranes has become a promising technique to deal with this problem; however, the scientific community, in the need to find better pesticide retention results, has begun to meddle in the functionalization of polymeric membranes. Given the great variety of membrane, polymer, and nanomaterial synthesis methods present in the market, the possibilities of obtaining membranes that adjust to different variables and characteristics related to a certain pesticide are relatively extensive, so it is expected that this technology will represent one of the main pesticide removal strategies in the future. In this direction, this review focused on, - the main characteristics of the nanomaterials and their impact on pristine polymeric membranes; - the removal performance of functionalized membranes; and - the main mechanisms by which membranes can retain pesticides. Based on these insights, the functionalized polymeric membranes can be considered as a promising technology in the removal of pesticides since the removal performance of this technology against pesticide showed a significant increase. Obtaining membranes that adjust to different variables and characteristics related to a certain pesticide are relatively extensive, so it is expected that functionalized membrane technology will represent one of the main pesticide removal strategies in the future.

Pyrolysis behavior, kinetics, and thermodynamics of waste pharmaceutical blisters under CO2 atmosphere.

The disastrous impact of COVID-19 pandemic has caused a significantly increased production and use of pharmaceutical drugs, which is accompanied by the rapid generation of waste pharmaceutical blisters (WPBs). Nonetheless, its treatment has not gained appropriate attentions and a perceptible process development was not achieved. In this study, the WPBs pyrolysis in CO2 atmosphere was conducted as well as the thermodynamics and kinetics were investigated. The thermogravimetric analysis revealed that the WPBs decomposition could be divided into two stages of 25 - 365 °C and 365 - 900 °C with mass loss of 56.5 - 60.5 wt% and 22.5 - 25.9 wt%, respectively. Fourier-transform infrared spectroscopy analysis indicated the dechlorination process initiating at ∼300 °C. The simultaneous asymmetric stretching of HCl and stretching vibration of C-Cl bond was detected in the range of 2600 - 3250 cm-1 and 660 - 750 cm-1, respectively. The dechlorination reactions were almost complete at ∼520 °C and minor peaks (2900 -3100 cm-1) due to C-H vibrations were observed. Gas chromatography-mass spectrometry analysis indicated that the evolved products included alkanes, benzene, olefin, as well as HCl. The cycloalkenes content significantly increased during the second conversion stage, implying the addition reactions between alkanes and olefins. The apparent activation energy was calculated using three model-free methods and the values from Flynn-Wall-Ozawa model increased from 142.0 to 255.8 kJ·mol-1 with an average value of 147.4 kJ·mol-1. The methods of Coats-Redfern as well as Malek were applied to determine the reaction mechanism. The one-dimensional diffusion model was more reliable to describe the WPBs pyrolysis. This study will represent a significant reference case for the thermochemical conversion of multilayer packing waste and facing the increasing demand for the medical waste recycling.

Fluorinated metal-organic frameworks for gas separation.

Fluorinated metal-organic frameworks (F-MOFs) as fast-growing porous materials have revolutionized the field of gas separation due to their tunable pore apertures, appealing chemical features, and excellent stability. A deep understanding of their structure-performance relationships is critical for the synthesis and development of new F-MOFs. This critical review has focused on several strategies for the precise design and synthesis of new F-MOFs with structures tuned for specific gas separation purposes. First, the basic principles and concepts of F-MOFs as well as their structure, synthesis and modification and their structure to property relationships are studied. Then, applications of F-MOFs in adsorption and membrane gas separation are discussed. A detailed account of the design and capabilities of F-MOFs for the adsorption of various gases and the governing principles is provided. In addition, the exceptional characteristics of highly stable F-MOFs with engineered pore size and tuned structures are put into perspective to fabricate selective membranes for gas separation. Systematic analysis of the position of F-MOFs in gas separation revealed that F-MOFs are benchmark materials in most of the challenging gas separations. The outlook and future directions of the science and engineering of F-MOFs and their challenges are highlighted to tackle the issues of overcoming the trade-off between capacity/permeability and selectivity for a serious move towards industrialization.

Low-dimensional heterostructures for advanced electrocatalysis: an experimental and computational perspective.

Low dimensional electrocatalytic heterostructures have recently attracted significant attention in the catalysis community due to their highly tuneable interfaces and exciting electronic features, opening up new possibilities for effective nanometric control of both the charge carriers and energetic states of several intermediate catalytic species. In-depth understanding of electrocatalytic routes at the interface between two or more low-dimensional nanostructures has triggered the development of heterostructure nanocatalysts with extraordinary properties for water splitting reactions, NRR and CO2RR. This tutorial review provides an overview of the most recent advances in synthetic strategies for 0D-1D, 0D-2D, and 2D-2D nanoheterostructures, discussing key aspects of their electrocatalytic performances from experimental and computational perspectives as well as their applications towards the development of overall water splitting and Zn-air battery devices.

Correction: Metal-organic framework (MOF)-, covalent-organic framework (COF)-, and porous-organic polymers (POP)-catalyzed selective C-H bond activation and functionalization reactions.

Correction for 'Metal-organic framework (MOF)-, covalent-organic framework (COF)-, and porous-organic polymers (POP)-catalyzed selective C-H bond activation and functionalization reactions' by Saba Daliran et al., Chem. Soc. Rev., 2022, https://doi.org/10.1039/d1cs00976a.